Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment

Definitions

• the present invention relates to a liquid crystal alignment agent containing polysiloxane obtained by polycondensation of alkoxysilane, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
• VA liquid crystal display elements are widely used for large-screen liquid crystal televisions and high-definition mobile applications (display units of digital cameras and mobile phones).
• the VA method includes an MVA method (Multi Vertical Alignment) in which protrusions for controlling the direction in which the liquid crystal is tilted are formed on the TFT substrate or the color filter substrate, and a direction in which the liquid crystal is tilted by forming an slit in the ITO electrode of the substrate.
• MVA method Multi Vertical Alignment
• a PVA (Paterned Vertical Alignment) system to be controlled is known.
• PSA Polymer Sustained Alignment
• the PSA system is a technology that has attracted attention in recent years.
• a photopolymerizable compound is usually added to a liquid crystal, and after producing a liquid crystal panel, an electric field is applied to irradiate the liquid crystal with ultraviolet rays (UV) while the liquid crystal is tilted.
• UV ultraviolet rays
• the polymerizable compound is photopolymerized to fix the alignment direction of the liquid crystal, causing a pretilt and improving the response speed.
• a slit is formed in one electrode constituting the liquid crystal panel, and the electrode pattern on the opposite side can operate even in a structure in which no protrusion in the MVA method or a slit in the PVA method is provided. It has features that simplification of production and excellent panel transmittance can be obtained (see Patent Document 1).
• inorganic liquid crystal alignment film materials are also known along with conventionally used organic liquid crystal alignment film materials such as polyimide.
• a composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid is used as a material for a coating-type inorganic alignment film, and is vertically aligned on an electrode substrate of a liquid crystal display element. It has been reported that a liquid crystal alignment film having excellent alignment properties, heat resistance and uniformity is formed (see Patent Document 2).
• liquid crystal aligning agent composition containing a tetraalkoxysilane, a specific trialkoxysilane and a reaction product with water, and a specific glycol ether solvent, display defects can be prevented and even after long-time driving. It has been reported that a liquid crystal alignment film is formed without leaving an afterimage, without reducing the ability to align liquid crystal, and with little reduction in voltage holding ratio against light and heat. (See Patent Document 3)
• JP 2004-302061 A JP 09-281502 A JP 2005-250244 A
• the object of the present invention is to improve the response speed and achieve good alignment even when the amount of the polymerizable compound added to the liquid crystal in the PSA method is small, and even when the liquid crystal without adding the polymerizable compound is used.
• An object of the present invention is to provide a liquid crystal aligning agent for a liquid crystal display element, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film capable of obtaining a state.
• a liquid crystal aligning agent for a device comprising polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2) .
• R 1 Si (OR 2 ) 3 (1) R 1 is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom, and R 2 represents an alkyl group having 1 to 5 carbon atoms.
• R 3 represents a hydrocarbon group having 1 to 18 carbon atoms
• R 4 represents an alkyl group having 1 to 5 carbon atoms.
• polysiloxane according to any one of [1] to [3], wherein the polysiloxane is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (4): Liquid crystal aligning agent.
• R 5 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group
• R 6 represents an alkyl group having 1 to 5 carbon atoms
• n represents an integer of 0 to 3.
• the polysiloxane contains 0.1 to 30 mol% of the alkoxysilane represented by the formula (1) in all alkoxysilanes, and the alkoxysilane represented by the formula (2) in all alkoxysilanes.
• the liquid crystal aligning agent according to any one of [1] to [8] is applied, and UV is irradiated in a state where a voltage is applied to a liquid crystal cell in which the liquid crystal is sandwiched between two baked substrates. Liquid crystal display element.
• liquid crystal aligning agent of the present invention even when the amount of the polymerizable compound added to the liquid crystal in the PSA method is small, or when using the liquid crystal without adding the polymerizable compound, the response speed is improved and good.
• a liquid crystal alignment film for a liquid crystal display element capable of obtaining an alignment state and a display element having the liquid crystal alignment film are obtained.
• the present invention is a liquid crystal aligning agent for PSA system containing a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2).
• R 1 Si (OR 2 ) 3 (1)
• R 1 is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom, and R 2 represents an alkyl group having 1 to 5 carbon atoms.
• “may be substituted” means “substituted or not substituted”.
• R 3 represents a hydrocarbon group having 1 to 18 carbon atoms
• R 4 represents an alkyl group having 1 to 5 carbon atoms.
• R 1 (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1) is a hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms which may be substituted with fluorine. There is no particular limitation as long as it has the effect of vertically aligning the liquid crystal. Examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a styrylalkyl group, a naphthyl group, and a fluorophenylalkyl group.
• alkoxysilanes in which R 1 is an alkyl group or a fluoroalkyl group are preferable because they are relatively inexpensive and easily available as commercial products.
• alkoxysilane in which R 1 is an alkyl group is preferable.
• the polysiloxane used in the present invention may have a plurality of these specific organic groups.
• R 2 of the alkoxysilane represented by the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, R 2 is a methyl group or an ethyl group. Although the specific example of the alkoxysilane represented by this Formula (1) is given, it is not limited to this.
• octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane Heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltriethoxysilane, or undecyltrimethoxysilane is preferred.
• the above-mentioned alkoxysilane represented by the formula (1) having a specific organic group is preferably 0.1 mol% or more in order to obtain good liquid crystal alignment in all alkoxysilanes used for obtaining polysiloxane. More preferably, it is 0.5 mol% or more. More preferably, it is 1 mol% or more. Further, in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed, 30 mol% or less is preferable. More preferably, it is 22 mol% or less.
• R 3 of the alkoxysilane represented by the formula (2) is a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. Hydrogen; ring structures such as aliphatic ring, aromatic ring and hetero ring; and hetero atoms such as oxygen atom, nitrogen atom and sulfur atom may be contained.
• An alkylene group and a phenylene group are preferred.
• the alkylene group has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms.
• the phenylene group is represented by the following formula (3), and m and n are each an integer of 0 to 6, preferably an integer of 0 to 2.
• R 4 of the alkoxysilane represented by the formula (2) is the same as the definition of R 2 in the above formula (1), and a preferable group of R 4 is the same as that of R 2 .
• alkoxysilane represented by Formula (2) is not limited to these.
• the alkoxysilane represented by the formula (2) having two specific organic groups is preferably 3 mol% or more in all alkoxysilanes used for obtaining the polysiloxane. More preferably, it is 5 mol% or more. More preferably, it is 10 mol% or more. Moreover, in order to fully harden the liquid crystal aligning film formed, 70 mol% or less is preferable.
• the alkoxysilane represented by the formula (1) is preferably contained in the total alkoxysilane used in an amount of 0.1 to 30 mol%, particularly preferably 2 to 20 mol%, and the formula (2) Is preferably 3 to 70 mol%, particularly preferably 5 to 30 mol%, based on the total alkoxy silane used.
• the alkoxysilane represented by following formula (4) can also be used besides the alkoxysilane represented by Formula (1) and Formula (2). Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
• R 5 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group.
• R 6 represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n represents an integer of 0 to 3, preferably 0 to 2.
• R 5 of the alkoxysilane represented by the formula (4) is a hydrogen atom or an organic group having 1 to 6 carbon atoms (hereinafter also referred to as a third organic group).
• third organic groups include aliphatic hydrocarbons; ring structures such as aliphatic rings, aromatic rings, and heterocycles; unsaturated bonds; heteroatoms such as oxygen, nitrogen, and sulfur atoms Or an organic group having 1 to 6 carbon atoms, which may have a branched structure. This organic group may be substituted with a halogen atom, amino group, glycidoxy group, mercapto group, isocyanate group, ureido group or the like.
• alkoxysilane represented by Formula (4) is not limited to this.
• specific examples of alkoxysilane when R 5 is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and the like.
• alkoxysilane of the formula (4) specific examples of the alkoxysilane when R 5 is a third organic group include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane.
• the polysiloxane used in the present invention is a kind of the alkoxysilane represented by the above formula (4) as long as the effects of the present invention are not impaired for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules. Or you may have multiple types.
• the alkoxysilane represented by the formula (4) the alkoxysilane in which n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formulas (1) and (2).
• alkoxysilane in which n is 0 in the formula (4) tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
• the amount of the alkoxysilane represented by the formula (4) is 10 to 96.9 mol% in the total alkoxysilane used for obtaining the polysiloxane. It is preferable that More preferably, it is 35 to 99.8 mol%.
• the method for obtaining the polysiloxane used in the present invention is not particularly limited. In the present invention, it is obtained by condensing an alkoxysilane having the above-mentioned formulas (1) and (2) as essential components in an organic solvent. Usually, polysiloxane is obtained as a solution obtained by polycondensation of such alkoxysilanes and uniformly dissolved in an organic solvent.
• a method for polycondensation of polysiloxane for example, a method of hydrolyzing and condensing alkoxysilane in a solvent such as alcohol or glycol can be mentioned. At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis.
• the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
• acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid and fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine
• alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine
• a metal salt such as hydrochloric acid, sulfuric acid or nitric acid
• a method of heating and polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. In that case, the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. Preferably, it is a method of heating for several tens of minutes to several tens of hours under reflux so that evaporation or volatilization of the liquid does not occur.
• the solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even when alkoxysilane does not melt
• Such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1 , 5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, and other glycols: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether Ethylene glycol monobutyl ether
• the polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method has a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). Is preferably 20% by mass or less, more preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
• the polymerization solution obtained by the above method may be used as a polysiloxane solution as it is, or if necessary, the solution obtained by the above method may be concentrated or diluted by adding a solvent. Or may be substituted with another solvent to form a polysiloxane solution.
• the solvent to be used hereinafter also referred to as additive solvent
• the additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
• Such an additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent described above, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate. Can be mentioned. These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.
• inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in the state of a colloidal solution are particularly preferable.
• This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution.
• the surface shape of the formed cured film can be changed or other functions can be imparted.
• the inorganic fine particles preferably have an average particle size of 0.001 to 0.2 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
• the dispersion medium for the inorganic fine particles include water and organic solvents.
• the colloidal solution it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating solution for forming a film. More preferably, it is 2-7.
• organic solvent used for the dispersion medium of the colloidal solution examples include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion
• metalloxane oligomer and metalloxane polymer single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
• the metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from monomers such as metal alkoxides, nitrates, hydrochlorides and carboxylates by a conventional method such as hydrolysis.
• metalloxane oligomers and metalloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
• siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
• titanoxane oligomers such as polymers and titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
• a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
• the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.
• the liquid crystal aligning agent of this invention is the solution containing the polysiloxane mentioned above and other components as needed.
• a solvent selected from the group consisting of the above-mentioned polysiloxane polymerization solvent and additive solvent is used.
• the content of polysiloxane in the liquid crystal aligning agent is preferably 0.5 to 15% by mass, more preferably 1 to 6% by mass in terms of SiO 2 equivalent concentration. Be in the range of such terms of SiO 2 concentration, easy to obtain a desired film thickness by a single coating, easy pot life sufficient solution is obtained.
• the method for preparing the liquid crystal aligning agent of the present invention is not particularly limited.
• the polysiloxane used in the present invention may be in a state where other components added as necessary are uniformly mixed.
• polysiloxane since polysiloxane is polycondensed in a solvent, it is convenient to use the polysiloxane solution as it is or to add other components to the polysiloxane solution as required.
• the most convenient method is to use the polysiloxane polymerization solution as it is.
• the solvent chosen from the group which consists of the polymerization solvent of polysiloxane mentioned above, and an addition solvent can be used.
• the liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent of this invention.
• the cured film obtained by drying and baking can also be used as a liquid crystal aligning film as it is.
• the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, processed with an ion beam, etc., or irradiated with UV in a state where a voltage is applied to the liquid crystal display element after filling the liquid crystal. It is also possible.
• the liquid crystal aligning agent of the present invention is useful both in the case of the PSA system in which a polymerizable compound is added to the liquid crystal and in the case where the polymerizable compound is not added to the liquid crystal.
• the substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving liquid crystal is formed on the substrate is preferable.
• the substrate include glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile.
• a substrate in which a transparent electrode is formed on a plastic plate such as triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose.
• the method for applying the liquid crystal aligning agent include spin coating, printing, ink jet, spraying, roll coating, and the like.In terms of productivity, the transfer printing method is widely used industrially.
• the present invention is also preferably used.
• the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred.
• the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like.
• a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.
• the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
• the firing temperature can be any temperature of 100 ° C. to 350 ° C., preferably 140 ° C. to 300 ° C., more preferably 150 ° C. to 230 ° C., and still more preferably 160 ° C. to 220 ° C. It is. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. The time is preferably 10 to 90 minutes, more preferably 20 to 90 minutes.
• a generally known method such as a hot plate, a hot air circulation oven, an IR (infrared) oven, a belt furnace or the like can be used.
• the polysiloxane in the liquid crystal alignment film undergoes polycondensation in the firing step.
• firing is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the liquid crystal cell production process, such as curing of the sealant.
• the thickness of the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more, since the reliability of the liquid crystal display element can be easily obtained.
• the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large.
• the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method.
• a method is generally employed in which a pair of substrates on which a liquid crystal alignment film is formed are fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed.
• the size of the spacer used is 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
• the method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after the inside of the manufactured liquid crystal cell is decompressed, and a dropping method for sealing after dropping the liquid crystal.
• a liquid crystal to which a photopolymerizable compound is preferably added in a small amount (typically 0.2 to 1% by weight) can be used as the liquid crystal to be used.
• the applied voltage is 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
• the UV irradiation amount to be irradiated is 1 to 60 J, but is preferably 40 J or less.
• the smaller the UV irradiation amount the lowering of reliability due to the destruction of the members constituting the liquid crystal display can be suppressed, and the UV irradiation time It is preferable because the manufacturing tact can be increased by reducing.
• the liquid crystal aligning agent of this invention is used also with the liquid crystal display element to which a polymeric compound is not added.
• the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed.
• a specific example is the same as the substrate described in [Liquid crystal alignment film].
• a PSA type liquid crystal cell a standard electrode pattern such as PVA or MVA or a protrusion pattern can be used for the substrate.
• the PSA type liquid crystal display can operate even in a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m is formed on one side substrate and no slit pattern or projection pattern is formed on the opposite substrate.
• the liquid crystal display can simplify the manufacturing process and obtain high transmittance.
• a high-performance element such as a TFT type element
• an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
• a transmissive liquid crystal element it is common to use a substrate as described above.
• an opaque substrate such as a silicon wafer can be used if only one substrate is used. It is. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
• TEOS tetraethoxysilane
• C18 octadecyltriethoxysilane
• VTES vinyltriethoxysilane
• ARMS allyltrimethoxysilane
• OTMS octenyltrimethoxysilane
• STMS styryltrimethoxysilane
• HG 2-methyl-2,4-pentanediol : Hexylene glycol
• BCS 2-butoxyethanol UPS: 3-ureidopropylethoxysilane
• the solution was stirred for 30 minutes and then refluxed for 1 hour, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG and 0.1 g of BCS was added in advance.
• the mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
• the solution was stirred for 30 minutes and then refluxed for 1 hour, and a mixed solution of 1.2 g of a methanol solution having a UPS content of 92% by mass, 0.6 g of HG and 0.2 g of BCS was added in advance.
• the mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
• the solution was stirred for 30 minutes and then refluxed for 1 hour, and a mixed solution of 1.2 g of a methanol solution having a UPS content of 92% by mass, 0.6 g of HG and 0.2 g of BCS was added in advance.
• the mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
• the solution was stirred for 30 minutes and then refluxed for 1 hour, and then allowed to cool to obtain a polysiloxane solution having a solid content concentration of 12% by weight as SiO 2 .
• the obtained polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO 2 concentration of 4 wt% of the liquid crystal alignment agent (L1).
• the solution was stirred for 30 minutes and then refluxed for 1 hour, and a mixed solution of 1.2 g of a methanol solution having a UPS content of 92% by mass, 0.6 g of HG and 0.2 g of BCS was added in advance.
• the mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
• Example 1 The liquid crystal aligning agent [K1] obtained in Synthesis Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m was formed. After drying on an 80 ° C. hot plate for 5 minutes, baking was performed in a hot air circulation oven at 180 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. The liquid crystal aligning agent [K1] obtained in Synthesis Example 1 is spin-coated on the ITO surface on which no electrode pattern is formed, dried on an 80 ° C. hot plate for 5 minutes, and then heated in a 180 ° C.
• a liquid crystal cell was prepared by injecting the liquid crystal MLC-6608 (trade name, manufactured by Merck) into the empty cell by vacuum injection.
• the response speed characteristics of these liquid crystal cells were measured by the method described later. Thereafter, UV (wavelength: 280 to 330 nm) was irradiated by 20 J from the outside of the liquid crystal cell in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell. Thereafter, the response speed characteristic was measured again, and the response speed before and after UV irradiation was compared. The results are shown in Table 1.
• Example 2 A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [K2] obtained in Synthesis Example 2, and the response speed was measured. The results are shown in Table 1.
• Example 3 A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [K3] obtained in Synthesis Example 3, and the response speed was measured. The results are shown in Table 1.
• the response speed was improved after UV irradiation even when the liquid crystal to which no polymerizable compound was added was used.
• the response speed did not improve before and after UV irradiation.
• the liquid crystal aligning agent of the present invention can improve the response speed and obtain a good alignment state even in the case of a PSA system in which a polymerizable compound is added to the liquid crystal or a liquid crystal in which no polymerizable compound is added.
• the liquid crystal display element produced using the liquid crystal aligning agent of this invention is useful as a TFT liquid crystal display element, a TN liquid crystal display element, a VA liquid crystal display element, etc.

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